CN107207758A

CN107207758A - Phenol resin foam and its manufacture method

Info

Publication number: CN107207758A
Application number: CN201680009535.2A
Authority: CN
Inventors: 浜岛雅人; 向山滋美; 井原健; 三堀寿; 深泽義人
Original assignee: Asahi Kasei Construction Materials Corp
Current assignee: Asahi Kasei Construction Materials Corp
Priority date: 2015-03-24
Filing date: 2016-03-23
Publication date: 2017-09-26
Also published as: EP3275925A4; TW201638198A; US20180044494A1; JPWO2016152154A1; KR20210029303A; AU2016237952A1; KR20170099964A; EP3275925A1; AU2016237952B2; RU2673528C1; JP2017226854A; EP3677623A1; EP3275925B1; KR102190552B1; CA2978851A1; TWI655237B; WO2016152154A1; CA2978851C; KR20190065490A; JP6208399B2

Abstract

The purpose of the application be there is provided the load caused to environment is small, compressive strength is high and treatability during construction and it is fixed when the excellent phenol resin foam of the cost that expends and its manufacture method.The phenol resin foam of the application is characterised by, containing at least one kind of in the group being made up of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons, and density is 20kg/m³Above and 100kg/m³Hereinafter, separated foam rate is more than 80% and less than 99%, and 10% compressive strength meets the relation of following formula with aforementioned densities.(in formula, C represents 10% compressive strength (N/cm to C >=0.5X 7²), X represents density (kg/m³))。

Description

Phenol resin foam and its manufacture method

Technical field

The present invention relates to phenol resin foam and its manufacture method.

Background technology

In recent years, the gas of house is required due to the raising of the related consciousness of energy-conservation and obligationization etc. of energy conservation standard of future generation The raising of close performance, heat-insulating property.The thickness of heat-insulating material needed for expecting can with this raising house air-tightness and The requirement of heat-insulating property and increase, but compressing due to indoor living space, the space in wall body are limited, therefore produce with exhausted The problem of thickness of hot material increases and needs design for change.

Herein, as the heat-insulating material of domestic use, it is known that the fiber system heat-insulating material headed by mineral wool, asbestos；Make Styrene resin, carbamate resins, the foamed plastic system heat-insulating material of Foaming of phenolic resin.Wherein, phenolic resin Foaming body is the excellent heat-insulating material for the domestic use that gas permeability is low, heat-insulating property is not susceptible to change in a long time.In addition, The heat-insulating property of known phenol resin foam can be because being significantly affected the species, state of the compound included in bubble.

Also, in the past as the above-claimed cpd used in phenol resin foam, use the CFC that thermal conductivity is low (CFC).But, CFC clearly results in the destruction of ozone layer, climatic fluctuation, therefore is discussed and decided based on the Montreal that 1987 use Book and abrogate and use.As a result, as above-claimed cpd, then use relatively low HFC (HFC) of ozone destruction coefficient etc..So And, it still has higher global warming coefficient, therefore, it is desirable to which CFC, HFC such ground thermal conductivity are low, ozone destruction coefficient is low And the low compound of global warming coefficient.

In patent document 1, patent document 2, patent document 3, patent document 4, as ozone destruction coefficient is low, global warming Coefficient is low and belongs to the compound of anti-flammability, discloses chloro or non-chloro HF hydrocarbon.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Application Publication 2010-522819 publications

Patent document 2：Japanese Unexamined Patent Publication 2013-064139 publications

Patent document 3：Japanese Unexamined Patent Publication 2011-504538 publications

Patent document 4：Japanese Unexamined Patent Publication 2007-070507 publications

The content of the invention

Problems to be solved by the invention

Patent document 1, patent document 2, patent document 3, patent document 4 discloses that a variety of chloros or non-chloro hydrogen fluorine alkene Hydrocarbon, wherein 1- chloro-3,3,3 ,-trifluoropropenes, 1 are described, 3,3,3- tetrafluoro-1-propenes, 2,3,3,3- tetrafluoro-1-propenes, 1,1, Isosorbide-5-Nitrae, the ozone destruction coefficient and global warming coefficient of 4,4- hexafluoro -2- butylene is low, and then available for foamed plastic system heat insulating material Material.However, although these compound ozone destruction coefficients and the coefficient that warms are low, polarity is high, thus be accordingly used in Foaming of phenolic resin During body, exist and the phenolic resin with hydroxyl as hydrophilic radical is subjected to plasticized and causes compressive strength, separated foam rate The problem of reduction.Therefore, by the technology of the conventional phenol resin foam for having used hydrocarbon be merely substituted for above-mentioned chloro or During non-chloro HF hydrocarbon, compressive strength and low, the of poor quality foaming body of separated foam rate are formed sometimes.On the other hand, existing Technology in, need to improve the density of phenol resin foam to improve compressive strength, therefore produce following problems sometimes： Weight becomes big, and treatability during construction is deteriorated, and fixes phenol resin foam using other parts, body and causes cost high Rise.

Therefore, it is an object of the present invention to provide the load caused to environment small (ozone destruction coefficient and the coefficient that warms It is low), compressive strength high and treatability during construction with it is fixed when the excellent phenol resin foam of the cost that expends and its manufacture Method.

The solution used to solve the problem

Further investigation is repeated in the present inventor etc. to achieve these goals, as a result finds：By using specific Compound, and make density, separated foam rate and 10% compressive strength be in specific scope, can obtain what environment was caused Load is small, compressive strength is high and treatability during construction and it is fixed when the excellent phenol resin foam of the cost that expends so that Complete the present invention.

That is, the present invention provides a kind of phenol resin foam, it is characterised in that containing selected from by chloro HF hydrocarbon, non- At least one kind of in the group of chloro HF hydrocarbon and halogenated hydrocarbons composition, density is 20kg/m³Above and 100kg/m³Hereinafter, independent gas Bubble rate is more than 80% and less than 99%, and 10% compressive strength meets the relation of following formula with above-mentioned density.

C≥0.5X-7

(in formula, C represents 10% compressive strength (N/cm²), X represents density (kg/m³))

Preferably comprise above-mentioned halogenated hydrocarbons and selected from being made up of above-mentioned chloro HF hydrocarbon and above-mentioned non-chloro HF hydrocarbon Group in it is at least one kind of.

At least one kind of preferably choosing in the group being made up of above-mentioned chloro HF hydrocarbon and above-mentioned non-chloro HF hydrocarbon The free chloro- 3,3,3- trifluoro propenes of 1-, the chloro- 3,3,3- trifluoro propenes of 2-, 1,3,3,3- tetrafluoro-1-propenes, 2,3,3,3- tetra- are fluoro- It is at least one kind of in the group of 1- propylene and 1,1,1,4,4,4- hexafluoro -2- butylene composition.

Above-mentioned halogenated hydrocarbons is preferably isopropyl chloride.

It is preferred that also comprising the hydrocarbon that carbon number is less than 6.

Above-mentioned at least one kind of content in chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons is relative to upper The total amount for stating the hydrocarbon that chloro HF hydrocarbon, above-mentioned non-chloro HF hydrocarbon, above-mentioned halogenated hydrocarbons and above-mentioned carbon number are less than 6 is preferred For more than 30 mass %.

It is preferred that also including nitrogen-containing compound.

Above-mentioned nitrogen-containing compound be preferably selected from by urea, melamine, quinuclidine, pyridine, hexa and they Mixture composition group in compound.

The absolute value of size changing amount after 3 drying and watering cycles repeatedly of above-mentioned phenol resin foam is preferably 2.0mm Below.

Above-mentioned phenol resin foam according to JIS A 9511 (2003) 5.1.4 fragility obtained be preferably 50% with Under.

And then, the present invention provides a kind of phenol resin foam plywood, it is characterised in that in above-mentioned Foaming of phenolic resin There is facestock, above-mentioned facestock is respectively provided with gas permeability on 1st face of body and the 2nd face.

And then, the present invention provides a kind of manufacture method of phenol resin foam, it is characterised in that make in facestock containing Phenolic resin, surfactant, curing catalysts and selected from by chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons At least one kind of foaminess phenol resin composition in the group of composition is foamed and solidified, and is obtained by gel permeation chromatography The weight average molecular weight Mw of above-mentioned phenolic resin be more than 400 and less than 3000, the viscosity at 40 DEG C of above-mentioned phenolic resin is More than 1000mPas and below 100000mPas, the viscosity rate of climb constant of above-mentioned phenolic resin is 0.05 (1/ minute) Above and 0.5 (1/ minute) below, the density of above-mentioned phenol resin foam is 20kg/m³Above and 100kg/m³Hereinafter, it is above-mentioned The separated foam rate of phenol resin foam is more than 80% and less than 99%, and 10% compression of above-mentioned phenol resin foam is strong The above-mentioned density of degree and above-mentioned phenol resin foam meets the relation of following formula.

C≥0.5X-7

Preferably, the losstangenttanδ at 40 DEG C of above-mentioned phenolic resin is more than 0.5 and less than 40.0, and 60 Losstangenttanδ at DEG C is more than 2.0 and less than 90.0.

The effect of invention

The phenol resin foam of the present invention has an above-mentioned composition, therefore the load caused to environment is small, compressive strength is high, And treatability during construction and the cost expended when fixing are excellent.

In addition, according to the manufacture method of the phenol resin foam of the present invention, can easily manufacture with above-mentioned composition The phenol resin foam of the present invention.

Embodiment

Hereinafter, it is described in detail for present embodiment (hereinafter referred to as " present embodiment ").It should illustrate, this Invention is not limited to following embodiment.

The phenol resin foam of present embodiment contains selected from by chloro HF hydrocarbon, non-chloro HF hydrocarbon and halo At least one kind of in the group of hydrocarbon composition, density is 20kg/m³Above and 100kg/m³Hereinafter, separated foam rate be more than 80% and Less than 99%, 10% compressive strength meets the relation of following formula with above-mentioned density.

C≥0.5X-7

It should illustrate, in this specification, will be selected from sometimes by chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons group Into group at least one kind of compound or mixture be referred to as " compound α ".

Herein, due to the compound α ozone destruction coefficient that is included in the phenol resin foam of present embodiment and complete Ball warms, and coefficient is low, and therefore, the load that the phenol resin foam of present embodiment is caused to environment is small.

As above-mentioned chloro HF hydrocarbon or above-mentioned non-chloro HF hydrocarbon, it is not particularly limited, height from thermal conductivity, From the viewpoint of foaminess, preferably 1- chloro-3,3,3 ,-trifluoropropenes, 2- chloro-3,3,3 ,-trifluoropropenes, 1,3,3,3- tetra- fluoro- 1- propylene, 2,3,3,3- tetrafluoro-1-propenes, 1,1,1,4,4,4- hexafluoro -2- butylene etc..

In addition, as above-mentioned halogenated hydrocarbons, be not particularly limited, from the height of thermal conductivity, ozone destruction coefficient and warm and be Number height, from the viewpoint of boiling point, preferably the halogenated hydrocarbons comprising at least one protium, without two or more halogen atoms Halogenated hydrocarbons or the halogenated hydrocarbons without fluorine atom, more preferably isopropyl chloride.

Above-claimed cpd α can be included selected from the group being made up of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons In a kind of compound, can also combine comprising a variety of.

The phenol resin foam of present embodiment can further include hydrocarbon, carbon dioxide etc. (being preferably hydrocarbon).

As above-mentioned hydrocarbon, the hydrocarbon that such as carbon number is less than 6 can be included.That is, the phenol resin foam of present embodiment Except including at least one kind of chemical combination in the group for being selected from being made up of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons , can also be further comprising the hydrocarbon that carbon number is less than 6 outside thing.As the hydrocarbon that above-mentioned carbon number is less than 6, specifically, it can arrange Enumerate normal butane, iso-butane, cyclobutane, pentane, isopentane, pentamethylene, neopentane, n-hexane, isohexane, 2,2- dimethyl Butane, 2,3- dimethylbutanes, hexamethylene etc..Wherein, it is adapted to using pentanes such as pentane, isopentane, pentamethylene, neopentanes Class；Or, normal butane, iso-butane, the butanes of cyclobutane.Above-mentioned hydrocarbon may be used alone, can also be used in combination two kinds with On.

The phenol resin foam of present embodiment is not particularly limited, for example, can include by a kind of above-claimed cpd α shape Into single compound, comprising a variety of above-claimed cpd α or at least one kind of above-claimed cpd α and at least 1 can also be included The above-mentioned hydrocarbon planted.Wherein, the phenol resin foam of present embodiment preferably comprises halogenated hydrocarbons and selected from by chloro hydrogen fluorine alkene At least one kind of compound in the group of hydrocarbon and non-chloro HF hydrocarbon composition.In addition, small, only from mean cell diameter can be obtained From the viewpoint of vertical bubble rate and the high foaming body of compressive strength, the phenol resin foam of present embodiment is for example preferably comprised At least one kind of above-claimed cpd α and at least one kind of above-mentioned hydrocarbon (are particularly preferably used as comprising a kind or 2 kinds of above-claimed cpd α 1 composition and be used as the 2nd composition comprising above-mentioned hydrocarbon (the pentane class such as pentamethylene, isopentane)).

When in the phenol resin foam of present embodiment comprising the hydrocarbon that above-mentioned carbon number is less than 6, above-claimed cpd α's contains Amount is not particularly limited, from mean cell diameter is small, separated foam rate high, from the viewpoint of thermal conductivity step-down, for example, relative to Above-claimed cpd α and total amount (100 mass %) of the carbon number for less than 6 hydrocarbon, preferably more than 30 mass % (such as 30 mass % Above and below 100 mass %), more preferably more than 40 mass % and below 100 mass %, more preferably 50 mass % Above and below 100 mass %, especially preferably more than 60 mass % and below 100 mass %, particularly preferably 70 mass % Above and below 100 mass %, be most preferably more than 80 mass % and below 100 mass %.

In present embodiment, as reducing the methanal trapping of the formaldehyde amount exhaled from phenol resin foam Agent, in order to assign flexibility to phenol resin foam, can also add nitrogen-containing compound into phenolic resin.

As above-mentioned nitrogen-containing compound, it can use and be selected from by urea, melamine, quinuclidine, pyridine, hexa-methylene Compound in the group that tetramine and their mixture are constituted etc., is adapted to use urea.It is used as adding in addition to the nitrogen-containing compounds Plus agent, can add nitrogen, helium, argon gas, metal oxide, metal hydroxides, metal carbon oxide, talcum, kaolin, Cab-O-sil, silica sand, mica, calcium silicate powder, wollastonite, glass dust, bead, flying dust, silicon ash, graphite, aluminium powder etc..It is used as metal Oxide, can use calcium oxide, magnesia, aluminum oxide, zinc oxide etc., as metal hydroxides, can use hydroxide Aluminium, magnesium hydroxide, calcium hydroxide etc., as metal carbon oxide, can use calcium carbonate, magnesium carbonate, barium carbonate, zinc carbonate Deng.In addition, as additive in addition to the nitrogen-containing compounds, silane based compound, siloxane-based compound can also be added. They may be used alone, can also be used in combination.As aforementioned silane based compound, can use HMDS and Dimethoxydimethylsilane etc., as aforementioned silicone based compound, can use HMDO etc..Aforementioned silane Based compound, silicone compounds do not have polarity, and therefore, it is difficult to mixed with the phenolic resin with polarity.Therefore formed a large amount of Nuclei of bubbles, so as to obtain, bubble diameter is small, foam with high separated foam rate.Above-mentioned nitrogen-containing compound and except upper State the additive outside nitrogen-containing compound may be used alone, can also be used in combination it is two or more.

The density of phenol resin foam in present embodiment is 20kg/m³Above and 100kg/m³Below, it is preferably 20kg/m³Above and 70kg/m³Below, it is more preferably 20kg/m³Above and 40kg/m³Below, it is more preferably 22kg/m³With Upper and 35kg/m³Below, it is most preferably 23kg/m³Above and 28kg/m³Below.If density is less than 20kg/m³, then bubble chamber film It is relatively thin, therefore bubble chamber film is easily damaged in foaming, so as to be difficult to the separated foam structure for obtaining height, compressive strength extremely drops It is low.If in addition, density is higher than 100kg/m³, then the solid thermal conductance change from the solid constituent headed by resin is big, adiabatic Performance is reduced.

It should illustrate, above-mentioned density refers to determine by the method described in " (2) foam volume density " of aftermentioned (evaluation) Value.Above-mentioned density can be for example, by above-claimed cpd α, the ratio of above-mentioned hydrocarbon, the ratio of curing catalysts, blowing temperature, phenol Molecular weight, reaction speed, viscosity of phenolic resin of urea formaldehyde etc. are adjusted.

The present inventor etc. has found：Hydrocarbon in the conventional phenol resin foam comprising hydrocarbon is merely substituted for compound During α, the viscosity rising part quilt associated with the curing reaction of phenolic resin in the foamed solidification step of phenol resin foam High-compatibilities of the compound α in phenolic resin is offset, and the growth rate of bubble is relative to accelerate.Consequently found that：Only hydrocarbon is replaced During into compound α, it is difficult to treatability when obtaining compressive strength high and construction and it is fixed when the excellent phenolic aldehyde tree of the cost that expends Fat foaming body.Also, repeat to find during further investigation：Its reason becomes too high or mistake with separated foam rate, compressive strength It is low relevant.

And then, the present inventor etc. has found：Risen by using the Mw of manufacturing condition, especially particular range, viscosity, viscosity The phenolic resin of velocity constant, tan δ, can make the physics values such as separated foam rate, compressive strength be in specific scope, also, By meeting physics value, treatability when can obtain compressive strength high and construction and it is fixed when the excellent phenol of the cost that expends Urea formaldehyde foaming body.

The separated foam rate of phenol resin foam in present embodiment is more than 80% and less than 99%, is preferably More than 85% and less than 99%, be more preferably more than 88% and less than 99%, particularly preferably more than 90% and 99% with Under.If separated foam rate is too low, hydrocarbon, the compound α included in bubble is easily replaced by air, therefore after long-time Heat-insulating property be deteriorated, bubble chamber film it is easily damaged, cause compressive strength to reduce, it is not preferable.

It should illustrate, above-mentioned separated foam rate refers to by the side described in " (3) the separated foam rate " of aftermentioned (evaluation) The value that method is determined.Above-mentioned separated foam rate can for example, by the viscosity of phenolic resin, the species of above-claimed cpd α or above-mentioned hydrocarbon or Oven temperature when ratio, condition of cure, foamed solidification etc. is adjusted.

10% compressive strength of the phenol resin foam in present embodiment is not particularly limited, and phenol is improved within reason The intensity of urea formaldehyde foaming body, the density of phenol resin foam (do not make preponderance, do not make manufacturing cost too improve) Viewpoint is set out, such as preferably 6N/cm²Above and 50N/cm²Below, it is more preferably 8N/cm²Above and 50N/cm²Below, enter One step is preferably 10N/cm²Above and 40N/cm²Below, it is particularly preferably 12N/cm²Above and 40N/cm²Below, it is most preferably 15N/cm²Above and 40N/cm²Below.

It should illustrate, above-mentioned 10% compressive strength refers to by described in " (4) 10% compressive strength " of aftermentioned (evaluation) Method determine value.Above-mentioned 10% compressive strength can be for example, by the molecular weight of phenolic resin, viscosity, reaction speed, above-mentioned Species or ratio, condition of cure (addition of such as curing catalysts, heat time), the foamed strip of compound α or above-mentioned hydrocarbon Part (such as oven temperature), structure (bubble chamber film does not have porose structure) of foaming body etc. are adjusted.

On the phenol resin foam in present embodiment, from the intensity relative to compression and construction when processing Property and reduction it is fixed when spent cost from the viewpoint of, above-mentioned 10% compressive strength meets the pass of following formula with above-mentioned density System.

C≥0.5X-7

(in formula, C represents above-mentioned 10% compressive strength (N/cm²), X represents above-mentioned density (kg/m³))

Wherein, in terms of the cost consumed when the treatability and reduction when relative to the intensity of compression and construction are fixed From the viewpoint of further excellent, the left side (C) of above-mentioned formula is preferably bigger by more than 0.5 than the right (0.5X-7), it is more preferably big by 0.8 with It is upper, further preferably big by more than 1.0, particularly preferably big by more than 1.5.

If in addition, the relation and density that meet above-mentioned formula are 20kg/m³More than, then the excellent strength of foaming body, for Ground, the construction of flat roof have for the building of phenol resin foam, the situation of walking thereon when in construction, maintenance Under, the problem of phenol resin foam is less prone to surface indentation or produces cracking.

The absolute value of size changing amount after 3 drying and watering cycles repeatedly of phenol resin foam in present embodiment (absolute value of size changing amount) be preferably below 2.0mm, more preferably below 1.6mm, more preferably below 1.3mm, Most preferably below 1.0mm.If the absolute value of size changing amount is more than 2.0mm, after phenol resin foam is applied with In the case of causing phenol resin foam contraction because dry and wet is repeated, the junction surface of the heat-insulating shield formed by foaming body is opened Crack gap, cause the heat-insulating property of building to be damaged, it is not preferable.On the other hand, expanded in phenol resin foam In the case of, the junction surface of plate can swell, and cause that the flatness of wall is impaired, degraded appearance, and it is not preferable.

Should illustrate, the absolute value of above-mentioned size changing amount refer to by aftermentioned (evaluation) " (5) 3 dry and wets are followed repeatedly The value that method described in the absolute value of size changing amount after ring " is determined.The absolute value of above-mentioned size changing amount can pass through example Molecular weight or reaction speed, the species of above-claimed cpd α or above-mentioned hydrocarbon or ratio, the addition of curing catalysts such as phenolic resin Oven temperature etc. when hardening time, the foamed solidification of amount or phenolic resin is adjusted.

The fragility of phenol resin foam in present embodiment is preferably less than 50%, is more preferably less than 40%, enters One step is preferably less than 30%, especially preferably less than 20%, particularly preferably less than 15%, most preferably less than 10%.Such as Fruit fragility is more than 50%, then production cost is uprised, and it is not preferable.And then, it is processed into construction by phenol resin foam shape Into plate when, there is the tendency of the easy defect of foaming body, it is not preferable.

It should illustrate, above-mentioned fragility refers to the value determined by the method described in " (6) fragility " of aftermentioned (evaluation).On Stating fragility can be for example, by the presence or absence of additives such as the composition of phenolic resin, ratio, nitrogen-containing compound, plasticizer, phenolic resin The density of foaming body, crosslink density of phenolic resin in phenol resin foam etc. are adjusted.

Phenol resin foam in present embodiment can be for example, by making comprising phenolic resin and compound α (preferably Phenolic resin, surfactant, curing catalysts and compound α) foaminess phenol resin composition foamed and solidified To manufacture.Above-mentioned foaminess phenol resin composition can further include hydrocarbon, can also comprising nitrogen-containing compound, plasticizer, The additives such as fire retardant, auxiliary curing agent, silane based compound, siloxane-based compound.In addition, in order to more closely control foaming And curing rate, the plasticizer of phthalic acid ester etc can also be added.

The manufacture method of the phenol resin foam of present embodiment can be following manufacture methods：For example, in facestock Make the foaminess phenol resin composition containing phenolic resin, surfactant, curing catalysts and compound α foamed and Solidification, the weight average molecular weight Mw for the above-mentioned phenolic resin obtained by gel permeation chromatography is more than 400 and less than 3000, above-mentioned Viscosity at 40 DEG C of phenolic resin is more than 1000mPas and below 100000mPas, also, above-mentioned phenolic resin Viscosity rate of climb constant be 0.05 (1/ minute) more than and 0.5 (1/ minute) below.

Above-mentioned phenolic resin can be for example, by with the compound with phenyl and the compound with aldehyde radical or derivatives thereof Carrying out heating as raw material, and using base catalyst more than 40 DEG C and within the scope of less than 100 DEG C of temperature makes it polymerize and obtain Arrive.

As the above-mentioned compound with phenyl for preparing above-mentioned phenolic resin, such as phenol, isophthalic can be included Diphenol, catechol, orthoresol, metacresol or paracresol, dimethylbenzene phenols, ethylo benzene phenols, p-t-butyl phenol etc..Its In, preferably phenol, orthoresol, metacresol or paracresol, most preferably phenol., can also as the compound with phenyl Use the compound with 2 core phenyl.There is the compound of phenyl can be used alone or using two or more for these.

During using the two or more compounds with phenyl, " mole with the compound of phenyl " is used each Plant the summation of the mole of the compound with phenyl.In addition, when using the compound with 2 core phenyl, will have 2 core phenyl Compound molal quantity be multiplied by value obtained from 2 be used as with 2 core phenyl compound mole, calculate " have phenyl Compound mole ".

As above-mentioned compound with aldehyde radical for preparing above-mentioned phenolic resin or derivatives thereof, it can include for example Formaldehyde, PARA FORMALDEHYDE PRILLS(91,95), 1,3,5- trioxanes, four formaldehyde etc..Wherein, preferably formaldehyde and PARA FORMALDEHYDE PRILLS(91,95).These have the chemical combination of aldehyde radical Thing or derivatives thereof can be used alone or using two or more.

During using two or more compound with aldehyde radical or derivatives thereof, " there is the compound or its derivative of aldehyde radical The mole of thing " is the summation of the mole of the various compounds with aldehyde radical used or derivatives thereof.It should illustrate, use " mole with compound or derivatives thereof of aldehyde radical " during PARA FORMALDEHYDE PRILLS(91,95) using the weight by PARA FORMALDEHYDE PRILLS(91,95) used divided by Value obtained from 30 is calculated, and using 1, " mole with compound of aldehyde radical or derivatives thereof " during 3,5- trioxane makes Value obtained from being multiplied by 3 with the molal quantity by used 1,3,5- trioxane is calculated, and " has aldehyde radical using during four formaldehyde Compound or derivatives thereof mole " be multiplied by 4 using the molal quantity by four formaldehyde used obtained from value calculate.

For preparing above-mentioned phenolic resin, the above-mentioned compound with aldehyde radical or derivatives thereof relative to above-mentioned with benzene The mol ratio of the compound of base (has mole of mole/compound with phenyl of the compound of aldehyde radical or derivatives thereof Amount) be preferably more than 1.5 and less than 3, more preferably more than 1.6 and less than 2.7, more preferably more than 1.7 and 2.5 with Under, be most preferably more than 1.8 and less than 2.2.By making compound with aldehyde radical or derivatives thereof relative to phenyl The mol ratio of compound is more than 1.5, the intensity decreases of bubble chamber film when can suppress foaming, keeps phenol resin foam Intensity.In addition, the amount of the required compound with aldehyde radical or derivatives thereof is sufficient in order that phenol nucleus is cross-linked to each other, Neng Gouchong Ground is divided to be crosslinked, therefore, it is possible to improve the bubble film-strength of phenol resin foam, improve separated foam rate.By making to have Compound of aldehyde radical or derivatives thereof is less than 3 relative to the mol ratio of the compound with phenyl, easily enters phenolic resin Row crosslinking, it is possible to increase bubble film-strength, the raising separated foam rate of phenol resin foam.

" the method described in the weight average molecular weight Mw " of (7) phenolic resin by aftermentioned (evaluation) of above-mentioned phenolic resin And the weight average molecular weight Mw obtained using gel permeation chromatography be for example preferably more than 400 and less than 3000, more preferably 500 with It is upper and less than 3000, more preferably more than 700 and less than 3000, particularly preferably more than 1000 and less than 2700, it is optimal Elect more than 1500 and less than 2500 as.Substantial amounts of addition reaction portion is remained by making weight average molecular weight Mw be less than in 400, phenol nucleus Position, therefore heat release quantitative change into phenolic resin after mixing cured catalyst is big, therefore, because being selected from by chloro HF hydrocarbon, non- Chloro HF hydrocarbon and halogenated hydrocarbons composition group in it is at least one kind of and the phenolic resin of plasticized is changed into high temperature, viscosity is further Reduction.As a result, inducing the rupture of bubble, the reduction of separated foam rate when foaming and causing compressive strength to reduce.If in addition, Weight average molecular weight Mw does not become big fully, then phenolic resin bubble chamber film in foaming is not applied to sufficient stretching, therefore there is pressure The tendency of contracting intensity decreases.And then, as described above, easily occurring gas when causing foamed solidification because of the reduction of the viscosity of phenolic resin The unification of bubble, hole becomes many, forms the big foam of poor quality of mean cell diameter.If in addition, weight average molecular weight Mw is more than 3000, then the viscosity of phenolic resin become too high, therefore, it is difficult to obtain necessary expansion ratio, it is not preferable.Further, since phenol Low molecular weight compositions in urea formaldehyde tail off, therefore the heat reduction produced in the solidification of phenolic resin, will not carry out fully Curing reaction so that exist compressive strength reduction mystery.

Viscosity at 40 DEG C of above-mentioned phenolic resin is for example preferably more than 1000mPas and below 100000mPas. In addition, from improve separated foam rate, reduction mean cell diameter from the viewpoint of, more preferably more than 5000mPas and Below 50000mPas, particularly preferably more than 7000mPas and below 30000mPas.If the viscosity of phenolic resin Too low (when being, for example, less than 5000mPas), then unificationization occurs in foamed solidification for the nuclei of bubbles in phenolic resin, therefore deposits Become tendency too much in cell diameter.And then, bubble chamber film easily ruptures because of blow pressure, therefore presence causes separated foam The tendency that rate is deteriorated.If the viscosity of phenolic resin is too high (when being greater than 100000mPas), expansion rate is slack-off, because This can not obtain necessary expansion ratio, and it is not preferable.

It should illustrate, the viscosity at above-mentioned 40 DEG C refers to (8) " viscosity of the phenolic resin at 40 DEG C " by (evaluation) Described in method determine value.Viscosity at above-mentioned 40 DEG C can for example, by phenolic resin weight average molecular weight Mw or moisture Addition of rate, plasticizer etc. etc. is adjusted.

The viscosity rate of climb constant of above-mentioned phenolic resin is for example preferably more than 0.05 (1/ minute) and 0.5 (1/ minute) Below, be more preferably more than 0.05 (1/ minute) and 0.4 (1/ minute) below, more preferably it is more than 0.07 (1/ minute) and 0.35 (1/ minute) below, be most preferably 0.08 (1/ minute) more than and 0.3 (1/ minute) below.If the viscosity rate of climb is normal Number is less than 0.05 (1/ minute), then will not fully carry out the curing reaction of phenolic resin when foaming, thus bubbles burst and formed Foam of poor quality, causes compressive strength to reduce.And then, because the cross-linking reaction of phenolic resin will not be sufficiently carried out, therefore hair The intensity decreases of resin portion in foam, so that in the presence of the mystery for not exhibiting sufficient compressive strength.If raising speed in viscosity Spend constant and be more than 0.5 (1/ minute), then become too much in the associated reaction heat of the solidification of foaming initial stage and phenolic resin, cause this A little heat storages are in foaming body, blow pressure becomes too high, cause to induce the rupture of bubble, compressive strength reduction.

Should illustrate, above-mentioned viscosity rate of climb constant refer to by aftermentioned (evaluation) " (9) viscosity rate of climb is normal The value that method described in number " is determined.Above-mentioned viscosity rate of climb constant can be for example, by having benzene during novolak resin The species or ratio, the weight average molecular weight Mw of phenolic resin of the compound of base or compound with aldehyde radical or derivatives thereof, contain The addition of nitrogen compound, addition of curing catalysts etc. are adjusted.

Tan δ (loss angle tangent) at 40 DEG C of above-mentioned phenolic resin are not particularly limited, from separated foam rate and compression From the viewpoint of intensity, such as preferably more than 0.5 and less than 40.0, more preferably more than 0.5 and less than 35.0, further it is excellent Elect more than 0.5 and less than 30.0 as.

Tan δ (loss angle tangent) at 50 DEG C of above-mentioned phenolic resin are not particularly limited, from separated foam rate and compression From the viewpoint of intensity, such as preferably more than 1.25 and less than 65.0, more preferably more than 2.0 and less than 60.0, further Preferably more than 4.0 and less than 55.0.

Tan δ (loss angle tangent) at 60 DEG C of above-mentioned phenolic resin are not particularly limited, from separated foam rate and compression From the viewpoint of intensity, such as preferably more than 2.0 and less than 90.0, more preferably more than 2.0 and less than 80.0, further it is excellent Elect more than 4.0 and less than 70.0 as.

Wherein, the losstangenttanδ at preferably 40 DEG C of above-mentioned phenolic resin is more than 0.5 and less than 40.0 and 60 Losstangenttanδ at DEG C is losstangenttanδ at more than 2.0 and less than 90.0,40 DEG C, the loss angle at 50 DEG C Losstangenttanδ at tangent tan δ and 60 DEG C using temperature as transverse axis, the figure of the longitudinal axis is used as using losstangenttanδ It is more preferably in four sides formed by (40 DEG C, 0.5), (40 DEG C, 40.0), (60 DEG C, 2.0), (60 DEG C, 90.0) in table at this 4 points In on the side of shape (quadrangle that 4 points of coordinate is linked with line segment) or inner side, more than 40 DEG C and less than 60 DEG C of scope Losstangenttanδ further preferably locate in using temperature as transverse axis, using losstangenttanδ as the chart of the longitudinal axis In the quadrangle formed by (40 DEG C, 0.5), (40 DEG C, 40.0), (60 DEG C, 2.0), this 4 points of (60 DEG C, 90.0) (by 4 points of seat The quadrangle that mark is linked with line segment) side on or inner side.That is, losstangenttanδ at 40 DEG C, the loss at 50 DEG C Losstangenttanδ at angle tangent tan δ and 60 DEG C is being used as the longitudinal axis using temperature as transverse axis, using losstangenttanδ Be more preferably in chart between y=0.075x-2.5 straight line and y=2.5x-60 straight line or on each straight line, 40 DEG C with Losstangenttanδ in upper and less than 60 DEG C of scope is being used as the longitudinal axis using temperature as transverse axis, using losstangenttanδ Chart in further preferably in y=0.075x-2.5 straight line and y=2.5x-60 straight line between or each straight line on.

As using temperature as transverse axis, using losstangenttanδ as the chart of the longitudinal axis in above-mentioned 4 points, more preferably (40 DEG C, 0.5), (40 DEG C, 35.0), (60 DEG C, 2.0), (60 DEG C, 80.0), be most preferably (40 DEG C, 0.5), (40 DEG C, 30.0), (60 ℃、4.0)、(60℃、70.0)。

Even if phenolic resin viscosity is identical, behavior when it is heated can also occur because of the difference of cross-linked state, additive Change.Tan δ are the ratio between loss elastic modulus and storage modulus, therefore there are following tendencies：The value more it is big then foam when phenolic aldehyde Resin is easier to be stretched, and the value is smaller, and phenolic resin during foaming is more easily broken off.Therefore, if the loss angle of phenolic resin Tangent tan δ are more than above range, then the growth rate of bubble becomes too fast relative to blow pressure, so that cause to induce brokenly bubble, Separated foam rate, compressive strength reduction.Stretched in addition, being difficult to apply phenolic resin in foaming, therefore also there is performance not Go out the mystery of high compression-strength.If losstangenttanδ is less than above range, phenolic resin during foaming is easily broken off, Therefore phenol resin foam bubble chamber film, skeleton portion fractures so that exist structure become discontinuously, compressive strength reduce Tendency.

It should illustrate, in this specification, tan δ (loss angle tangent) refer to by aftermentioned (evaluation) " in (10) tan δ " The value that the method for record is determined.Above-mentioned tan δ can be for example, by the compound with phenyl during novolak resin, with aldehyde The species or ratio of the compound of base or derivatives thereof, the weight average molecular weight Mw of phenolic resin, the moisture rate in phenolic resin, increasing Additives such as agent etc. are moulded to adjust.

As above-claimed cpd α, above-claimed cpd can be included.

The content of above-claimed cpd α in above-mentioned foaminess phenol resin composition is not particularly limited, from thermal conductivity Viewpoint is set out, for example the total amount (100 mass %) relative to above-mentioned phenolic resin and above-mentioned surfactant, preferably 0.5 matter Measure more than % and below 25 mass %, more preferably more than 2 mass % and below 20 mass %, more preferably 3 mass % Above and below 18 mass %, particularly preferably more than 3 mass % and below 15 mass %.

In present embodiment, the total content of above-claimed cpd α and/or above-mentioned hydrocarbon is not particularly limited, such as relative to upper State the total amount (100 mass %) of phenolic resin and above-mentioned surfactant, preferably with more than 3.0 mass % and 25.0 mass % with Under scope be added, more preferably more than 3.0 mass % and below 22.5 mass %, more preferably 5.0 mass % Above and below 20.0 mass %, particularly preferably more than 6.0 mass % and below 18.0 mass %, be most preferably 6.0 matter Measure more than % and below 15.0 mass %.If addition is less than 3.0 mass %, it is very difficult to obtain necessary foaming times Rate, forms the too high foaming body of density, it is impossible to obtain good foaming body, it is not preferable.If addition is more than 25.0 matter % is measured, then the viscosity of phenolic resin is reduced because of compound α plasticized effect, also, because addition is excessive and produces excessive Foaming, the bubbles burst of foaming body, the reduction of separated foam rate, the physical property such as long-term insulation performance, compressive strength reduction, therefore unexcellent Choosing.

In present embodiment, in order to improve the reduction of the separated foam rate, compressive strength associated with phenolic resin plasticized, It is preferred that using as inorganic gas such as the nitrogen of bubble nucleating agent, argon gas in the total amount relative to above-claimed cpd α and/or above-mentioned hydrocarbon According to mass conversion for more than 0.05% and less than 5.0% scope in together added with compound α, more preferably 0.05% with It is upper and less than 3.0%, more preferably more than 0.1% and less than 2.5%, particularly preferably more than 0.1% and 1.5% with Under, be most preferably more than 0.3% and less than 1.0%.If addition is less than 0.05%, it can not give full play of as bubble The effect of nucleator, if addition is more than 5.0%, blow pressure becomes during the foamed solidification of phenol resin foam Obtain too high, therefore the bubble of foaming body is damaged, forms the low and of poor quality foaming body of separated foam rate, compressive strength, it is not preferable.

As above-mentioned nitrogen-containing compound, above-claimed cpd can be included.

, as is generally known, can be in the course of reaction of phenolic resin or terminal as above-mentioned nitrogen-containing compound Neighbouring time point is directly added, and material obtained from being reacted in advance with formaldehyde can also be mixed into phenolic resin.

The content of above-mentioned nitrogen-containing compound is not particularly limited, and has aldehyde radical from reduction from what phenol resin foam spread Compound or derivatives thereof, from the viewpoint of the flexibility of phenol resin foam, such as relative to above-mentioned phenolic resin Total amount (100 mass %), preferably more than 1 mass % and below 15 mass %, more preferably more than 2 mass % and 10 mass % Below, more than 3 mass % and below 8 mass % are particularly preferably.

As above-mentioned plasticizer, such as phthalate, the ethylene glycol for belonging to glycols, diethylene glycol can be included Deng, wherein, it is adapted to use phthalic acid ester.In addition it is possible to use aliphatic hydrocarbon or ester ring type hydrocarbon or their mixing Thing.Above-mentioned plasticizer may be used alone, can also be used in combination two or more.

As above-mentioned fire retardant, the tetrabromobisphenol A usually used for example as fire retardant, deca-BDE can be included Deng bromine compounds；Phosphorus or the phosphorus compounds such as aromatic phosphoric ester, aromatic series fusion phosphate, halogenated phosphate, red phosphorus；Polyphosphoric acid The antimonials such as ammonium, antimony trioxide, antimony pentaoxide.Above-mentioned fire retardant may be used alone, can also be used in combination two or more.

As above-mentioned surfactant, the surfactant for being commonly used to manufacture phenol resin foam can be used, its In, nonionic surfactants are effective, preferably for example as oxirane and the alkylidene of the copolymer of expoxy propane Oxide；The condensation product of alkylene oxide and castor oil；Alkylene oxide and nonyl phenol, dodecyl phenol etc The condensation product of alkylphenol；Polyoxyethylene alkyl ether and then polyoxyethylene fatty acid of the carbon number of alkyl ether moieties for 14~22 The fatty acid esters such as ester；The silicone compounds such as dimethyl silicone polymer；Polyalcohols etc..These surfactants can be independent Use, can also be applied in combination two or more.

The consumption of above-mentioned surfactant is not particularly limited, preferably using relative to the above-mentioned mass parts of phenolic resin 100 as Scope more than 0.3 mass parts and below 10 mass parts is used.

As above-mentioned curing catalysts, as long as the acid curing catalysts that can solidify phenolic resin, For example it is preferably acid anhydride curing agent.It is used as above-mentioned acid anhydride curing agent, preferably phosphoric anhydride, arylsulphonic anhydrides.As Above-mentioned arylsulphonic anhydrides, can include toluenesulfonic acid, xylene monosulfonic acid, phenolsulfonic acid, fortified phenol sulfonic acid, xylenols sulphur Acid, substituted dimethyl phenolsulfonic acid, DBSA, benzene sulfonic acid, naphthalene sulfonic acids etc., they can use one kind, can also group Close using two or more.Above-mentioned curing catalysts can be diluted with spent glycol, diethylene glycol equal solvent.

The consumption of above-mentioned curing catalysts is not particularly limited, preferably using relative to the above-mentioned mass parts of phenolic resin 100 as 3 Scope more than mass parts and below 30 mass parts is used.In addition, relative to above-mentioned phenolic resin and above-mentioned surfactant Total amount (100 mass parts), can be for more than 3 mass parts and below 30 mass parts.

As above-mentioned auxiliary curing agent, can include for example resorcinol, cresols, salicin (adjacent hydroxymethylphenol), to hydroxyl Methylphenol etc..Above-mentioned auxiliary curing agent may be used alone, can also be used in combination two or more.

Above-mentioned foaminess phenol resin composition is not particularly limited, can be for example, by by above-mentioned phenolic resin, above-mentioned table Face activating agent, above-claimed cpd α, above-mentioned hydrocarbon, above-mentioned curing catalysts, above-mentioned nitrogen-containing compound, above-mentioned plasticizer, other materials Obtained Deng being mixed.

Phenol resin foam can be obtained by the continuous mode of production comprised the steps：For example, by above-mentioned foaming Property phenol resin composition is continuously ejected in the facestock of walking, and foaminess phenol resin composition is covered with other facestocks The surface with contacting facestock be opposite side surface, also, make foaminess phenol resin composition foamed and heated consolidate Change.In addition, as other embodiments, can also be obtained by following Batch Process modes：By above-mentioned foaminess phenolic aldehyde Resin combination flows into the mould inframe that is covered by facestock of inner side or is coated with the mould inframe of releasing agent, and it is foamed Be heating and curing.As needed can also be along thickness side by phenol resin foam obtained from foregoing Batch Process mode To being cut into slices and used.

It should illustrate, in this specification, (the bag of plywood obtained from being laminated phenol resin foam in facestock sometimes Plywood containing facestock and phenol resin foam) it is referred to as phenol resin foam plywood.Phenol resin foam plywood There can be 1 facers, it is possible to have 2 facers are (on the 1st face of phenol resin foam on (upper surface) and the 2nd face The facestock (upper facestock and lower facestock) that (lower surface) is set).Above-mentioned facestock is preferably entered with the form for contacting phenol resin foam Row is set.

Above-mentioned facestock is not particularly limited, from what is produced when removing the foaming and solidification in foaminess phenol resin composition Moisture (middle moisture produced of moisture, curing reaction (dehydration condensation) included in phenolic resin etc.), prevents bag in bubble Containing water vapor, internal pressure become it is too high caused by brokenly bubble, further improve separated foam rate from the viewpoint of, be preferably for example have There is the facestock of gas permeability.As the above-mentioned facestock with gas permeability, such as polyester non-woven fabrics (poly terephthalic acid can be included Glycol ester non-woven fabrics etc.), non-woven fabrics of synthetic fiber, the glass fibre such as polyamide non-woven fabrics (nylon non-woven fabrics etc.) without Cloth, all-glass paper, stationery, the metallic film with through hole are spun (by metal foil and paper with through hole, glass cloth, glass Glass fiber is fitted and enhanced sandwich) etc..Wherein, from anti-flammability, facestock adhesive strength, prevent foaminess phenolic resin composition From the viewpoint of thing oozes out, preferably PET non-woven fabrics, glass fibre non-woven, the aluminium with through hole.It should illustrate, Metallic film with through hole can be manufactured by opening the processing of through hole etc. along thickness direction brill.Above-mentioned phenolic resin hair Foam plywood makes moisture easily be sent out from phenol resin foam by the facestock with gas permeability in foamed solidification Dissipate, therefore, it is possible to suppress bubble because of vapor brokenly bubble.From this point of view, above-mentioned phenol resin foam is preferably the 1st Face (upper surface) and the 2nd face (lower surface) have facestock, and 2 facers are gas permeability.

The gas permeability of above-mentioned facestock refers to that the oxygen transmission rate determined according to ASTM D3985-95 is 4.5cm³/24h·m²More than Facestock.

For example, in order to prevent facestock fracture during production, above-mentioned facestock preferably has flexibility.As with flexible face Material, can include such as non-woven fabrics of synthetic fiber, synthetic fibers weave cotton cloth, all-glass paper, fiberglass woven cloth, glass fibre without Spin cloth, glass fibre mixed copy paper, stationery, metallic film (metallic film with through hole) or combinations thereof etc..In order to Anti-flammability is assigned, above-mentioned facestock can contain fire retardant.As above-mentioned fire retardant, tetrabromobisphenol A, deca-BDE can be used Deng bromine compounds；Phosphorus or the phosphorus compounds such as aromatic phosphoric ester, aromatic series fusion phosphate, halogenated phosphate, red phosphorus；Polyphosphoric acid The antimonials such as ammonium, antimony trioxide, antimony pentaoxide；The metal hydroxides such as aluminium hydroxide, magnesium hydroxide；Calcium carbonate, sodium carbonate Deng carbonate.Above-mentioned fire retardant can be kneaded into the fiber of above-mentioned facestock, can also add acrylic compounds, polyvinyl alcohol, second In the binding agent of the facestocks such as vinyl acetate, epoxy, unsaturated polyester (UP).In addition, above-mentioned facestock can utilize fluororesin system, silicone resin Water repellent, the asphalt series waterproof finishing agents such as system, wax emulsion system, alkane hydrocarbon system, acrylic resin paraffin wax combined system enter Row surface treatment.These water repellents, waterproof finishing agent can be used alone, and can also add above-mentioned fire retardant and be coated on facestock On.

The temperature of above-mentioned foaminess phenol resin composition when spraying above-mentioned foaminess phenol resin composition in facestock Degree is for example preferably more than 25 DEG C and less than 50 DEG C, more preferably more than 30 DEG C and less than 45 DEG C.By making said temperature be 50 Below DEG C, foaming can be moderately produced, smooth foamed board can be obtained., can appropriateness by making said temperature be more than 25 DEG C Ground produces solidification, is produced with good balance and foams and solidify.

The foaming body phenol resin composition clamped by two facers can foam between two facers.In order that this is The phenol resin composition (foaming body) of foaming solidifies, can be with use example the first baking oven described as follows and the second baking oven.

First baking oven for example using ring steel belt type double type conveyer belt or strip type double type conveyer belt, more than 60 DEG C and Foamed, solidified in less than 110 DEG C of atmosphere.By the way that uncured foaming body is configured into tabular in the baking oven and makes it Solidification, can obtain partially cured foaming body.Can be uniform temperature with whole region in first baking oven, it is possible to have Multiple temperature provinces.

Second baking oven is preferred to produce more than 70 DEG C and less than 120 DEG C of hot blast, and makes to have carried out part in the first baking oven Solidify afterwards occur for the foaming body of solidification.Through partially cured foaming body plate sept, pallet can be used to enter at certain intervals Row is overlapping.If the temperature in the second baking oven is too high, the pressure inside the bubble of foaming body becomes too high, therefore induces broken Bubble, if temperature is too low, the excessive consuming time is possible in order to promote the reaction of phenolic resin, therefore more preferably 80 DEG C Above and less than 110 DEG C.

In addition, in the first baking oven, the second baking oven, the internal temperature of phenol resin foam be preferably more than 60 DEG C and Less than 105 DEG C, more preferably more than 70 DEG C and less than 100 DEG C, be more preferably more than 75 DEG C and less than 95 DEG C, most preferably More than 75 DEG C and less than 90 DEG C.The internal temperature of phenol resin foam can be for example, by the foaminess phenolic resin into baking oven Thermocouple and data recording function is put into composition to be measured.

During using compound α, phenolic resin is caused to be plasticized by high-compatibilities of the compound α in phenolic resin Change, thus the step of foamed solidification in have that the viscosity rising part associated with the curing reaction of phenolic resin be cancelled it is outstanding Read.As a result, when being heated in baking oven same as the prior art, there is phenol resin foam can not obtain abundant hardness Worry.Therefore, situation of the total retention time in the first baking oven and the second baking oven preferably than conventional use hydrocarbon is longer.As Total retention time in the first baking oven and the second baking oven, such as preferably more than 3 minutes and less than 60 minutes, more preferably 5 Minute more than and less than 45 minutes, particularly preferably more than 5 minutes and less than 30 minutes, most preferably more than 7 minutes and 20 points Below clock.If the holdup time in baking oven is too short, phenol resin foam is moved from baking oven in the uncured state Go out, therefore as poor dimensional stability and phenol resin foam of poor quality.If the holdup time in baking oven is long, phenol Urea formaldehyde foaming body overdrying, moisture content become too low, therefore move out of the moisture in rear a large amount of suction air from baking oven, deposit In the mystery of slab warping, it is not preferable.

It should illustrate, the hair of the foaminess phenol resin composition of the phenol resin foam for obtaining present embodiment Bubble and curing are not limited to the above method.

The phenol resin foam of the present invention can be used as the thermal insulation of such as residential building material purposes, industrial use or industrial applications Material etc..

More than, the manufacture method according to present embodiment, using the teaching of the invention it is possible to provide carrying capacity of environment is small, compressive strength is high and applies The treatability in the man-hour phenol resin foam excellent with the cost expended when fixing.

Embodiment

Hereinafter, the present invention is further illustrated based on embodiment and comparative example, but the present invention is not limited to following reality Apply example.

(evaluation)

For the phenolic resin in embodiment and comparative example, phenol resin foam, carry out the measure of following projects and comment Valency.

(1) compound α and/or the Identification of Species of hydrocarbon in phenol resin foam

First by the calibrating gas of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons, obtain following GC/MS and survey Retention time under fixed condition.

Facestock is peeled off from the phenol resin foam plywood obtained by embodiment and comparative example, by Foaming of phenolic resin Body sample about 10g and metal file put into 10L containers (product name " Tedlar Bag ") and sealed, and inject 5L nitrogen.From Tedlar Bag top is ground sample, fine crushing using file.Then, sample is put into Tedlar Bag shape Adjust to 81 DEG C of tempering machine and place 10 minutes in temperature under state.The gas produced in Tedlar Bag is taken into 100 μ L, profit Carry out GC/MS analyses with condition determination described below, thus identify above-claimed cpd α in phenol resin foam and/or The species of above-mentioned hydrocarbon.

The presence or absence of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons are confirmed according to GC/MS analysis result.Root The species of chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons is identified according to the retention time and mass spectrum obtained in advance.Pin To above-mentioned hydrocarbon, species is obtained according to retention time and mass spectrum.Produced gas is separately determined according to various calibrating gas The detection sensitivity of composition, is calculated according to using the detection zone area and detection sensitivity of the obtained each gas componants of GC/MS Go out ratio of components.The mass ratio of each gas componant is calculated according to the ratio of components and molal weight of each gas componant identified.

(GC/MS condition determinations)

Gas chromatography：" the Agilent7890 types " of Agilent Technologies companies manufacture

Post：The manufacture of GL Sciences companies " InertCap 5 " (and internal diameter be 0.25mm, thickness be 5 μm, length be 30m)

Carrier gas：Helium

Flow：1.1ml/ minute

The temperature of inlet：150℃

Method for implanting：Shunting (1:50)

The injection rate of sample：100μl

Column temperature：Kept for 5 minutes with -60 DEG C, be warming up to 150 DEG C with 50 DEG C/min, and kept for 2.8 minutes

Mass spectral analysis：" the Q1000GC types " of Jeol Ltd.'s manufacture

Ioning method：Electron ionization method (70eV)

Scanning range：M/Z=10~500

Voltage：-1300V

Ion source temperature：230℃

Interface temperature：150℃

(2) foam volume density

The plate of 20cm square is cut out from the phenol resin foam plywood obtained by embodiment and comparative example, face is removed Material, determines the quality and apparent volume of phenol resin foam.Using the quality and apparent volume obtained, according to JIS K 7222, calculate density (apparent density).

(3) separated foam rate

Using ASTM D 2856-94 (1998) A as reference, it is measured using following methods.

From the thickness of the phenol resin foam in the phenol resin foam plywood obtained by embodiment and comparative example Degree direction central portion cuts out the cube test piece of about 25mm square.25mm examination in uniform thickness can not be obtained in thinner thickness In the case of piece, the cube strip of the about 25mm square cut out is sliced into each about 1mm, had using thus obtained The test piece of uniform thickness.The length on each side is determined using slide measure, apparent volume (V1 is determined：cm³), and determine test piece Quality (W：4 effective digitals, g).Then, using air specific weight bottle (TOKYO SCIENCE. companies, trade name " MODEL1000 "), according to the method described in ASTM D 2856 A methods, determine the closing space volume (V2 of test piece：cm³)。

In addition, according to the assay method of above-mentioned (3) mean cell diameter, determining mean cell diameter (t：), also, root cm Surface area (the A of test piece is determined according to each edge lengths of above-mentioned test piece：cm²)。

According to t and A, the open volume of the cut-off bubble of strip is calculated by Formula V A=(A × t)/1.14 (VA：cm³).In addition, the density of solid phenolic resin is set into 1.3g/cm³, calculated by Formula V S=test pieces quality (W)/1.3 Volume (the VS of the solid portion of the composition walls included in test piece：cm³)。

Separated foam rate is calculated by following formula (1).

Separated foam rate (%)=((V2-VS)/(V1-VA-VS)) × 100 (1)

Determined 6 times for the foaming body sample of identical manufacturing condition, be averaged value as typical value.

(4) 10% compressive strengths

Long 100mm, width 100mm examination are cut out from the phenol resin foam plywood obtained by embodiment and comparative example Piece is tested, facestock is removed and obtains test film.Solidified gained test film, up in 23 DEG C of temperature, relative humidity 50% The difference of the value of weighing twice carried out in atmosphere with the interval of 24 hours reaches less than 0.1%.Obtained according to JIS K 7220 solid 10% compressive strength of the test film after change.

(5) absolute value of size changing amount repeatedly after 3 drying and watering cycles

Long 300mm, width 300mm examination are cut out from the phenol resin foam plywood obtained by embodiment and comparative example Piece is tested, facestock is removed and obtains test film.Gained test film is placed into 2 stars in 23 DEG C of temperature, the atmosphere of relative humidity 50% Phase.Thereafter the transverse direction (W) of determination test piece and the size of longitudinal direction (L), obtain size A during on-test_0W、A_0L.From experiment opening Begin in 12 hours, test film has been placed in temperature 50 C, the atmosphere of relative humidity 95%, from after 12 hours on-tests Untill after 24 hours, test film is placed in temperature 50 C, the atmosphere of relative humidity 35%.Will be from on-test to 24 As 1 circulation untill after hour, test film is placed untill 3 circulations terminate.3 circulation end are from on-test After 72 hours.The transverse direction (W) of test film of the measure after 3 circulations terminate, i.e. from on-test after 72 hours and longitudinal direction (L) Size, obtain A_72W、A_72L.The absolute value of the size changing amount after 3 drying and watering cycles is as following formula (2), (3) repeatedly Calculate.The absolute value of the size changing amount after 3 drying and watering cycles refers in the absolute value of size changing amount longitudinally, laterally repeatedly The greater.In addition, the vertical and horizontal of test body refer to the direction vertical with the thickness direction of product.

Repeatedly the absolute value of the horizontal size changing amount after 3 drying and watering cycles=| A_72W-A_0W| (2)

Repeatedly the absolute value of longitudinal size changing amount after 3 drying and watering cycles=| A_72L-A_0L| (3)

(6) fragility

Fragility is following to operate to calculate according to JIS A 9511 (2003) 5.1.4.Obtained from by embodiment and comparative example Phenol resin foam plywood peel the facestock on surface off, make 12 be stripped off with a surface comprising facestock after surface Mode cut into test film obtained from 25 ± 1.5mm cubic, with ± 1% precision determination quality.Experimental rig It is as follows：In the one side installation door of case, can be carried out in the way of dust is not leaked to outside case it is closed, internal diameter be 191 × 197 × The outside installation axle of the central portion in the 197mm faces of 197mm oak wooden case, can with it is per minute be that the rotating speed of 60 ± 2 times enters Row rotation.By 24 dried proportions be oak dice and test film that 0.65, size is 19 ± 0.8mm together put into Determine in device and closed, wooden case is rotated 600 ± 3 times.After rotation terminates, the inclusion of chest is carefully transferred to JIS Z 8801 screen cloth nominal size is online for 9.5mm's, is sieved and removes small pieces, taken and remain in online experiment Piece, and quality measurement.Fragility is obtained by following formula.

Fragility (%)=100 × (m₀-m₁)/m₀

(herein, m₀：The quality (g) of test film before experiment, m₁：The quality (g) of test film after experiment)

(7) the weight average molecular weight Mw of phenolic resin

Determined, be measured according to following such conditions by gel permeation chromatography (GPC), shown according to by aftermentioned The standard curve that standard substance (polystyrene standard, 2- hydroxy-benzyl alcohols and phenol) is obtained, obtain makes in embodiment and comparative example The weight average molecular weight Mw of phenolic resin.

Pre-treatment：

Phenolic resin about 10mg is dissolved in N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.'s system, efficient liquid phase Chromatographic grade) 1ml, is filtered using 0.2 μm of membrane filter, products therefrom is used as to determine solution.

Condition determination：

Determine device：Shodex System21 (Showa Denko K. K's system)

Post：Shodex asahipak GF-310HQ(7.5mmI.D.×30cm)

Eluent：The mass % of lithium bromide 0.1 is dissolved in N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.'s system, High performance liquid chromatography use) and use.

Flow：0.6ml/ minutes

Detector：RI detectors

Column temperature：40℃

Standard substance：Polystyrene standard (Showa Denko K. K's system, " Shodex standard SL-105 "), 2- Hydroxy-benzyl alcohol (Sigma-Aldrich company systems, 99% product), phenol (Kanto Kagaku K. K.'s system, superfine)

The viscosity of phenolic resin at (8) 40 DEG C

Phenolic resin 0.5ml is measured, being placed in rotation viscometer, (Toki Sangyo Co., Ltd.'s system, R-100 types, rotor portions are 3°×R-14).The viscosity for the phenolic resin to be determined reaches 50~80% scope with the determination of the upper limit viscosity relative to device Mode set the rotating speed of rotor.Temperature will be determined and be set to 40 DEG C, the viscosity number since determining after 3 minutes is regard as measure Value.

(9) viscosity rate of climb constant

In quality used in 10g embodiment and comparative example in phenolic resin, by the mass % of xylene monosulfonic acid 70 and The mass % of diethylene glycol 30 curing catalysts are relative to the mass % of phenolic resin precision weighing 10 and add, at 20 DEG C fully Mixing 1 minute.

The mixture 0.5ml of above-mentioned phenolic resin and curing catalysts is placed in rotation viscometer (eastern machine industry strain formula meeting Society's system, R-100 types, rotor portions are 3 ° × R-14), with the viscosity at 40 DEG C of the measuring space of 30 seconds.By the X-axis of measurement result The time (minute) since viscosimetric analysis is set to, Y-axis is set to viscosity (mPas) logarithm, single log-log plot is carried out. Time was regarded as straight line within 4 minutes to 10 minutes, obtained its " slope (1/ (minute) ".Should " slope " be denoted as " in viscosity Lifting speed constant ".

(10)tanδ

The aluminum that 50mm φ are installed on determination of viscoelasticity device (trade name " ARES ", TA Instruments systems) is parallel Template fixture.Among 2 parallel-plates setting up and down, phenolic resin about 2ml is set on the parallel-plate of downside.Thereafter, will The spacing of parallel-plate is set to 0.5mm, wipes the resin overflowed around parallel-plate off with spatula.Then, to surround parallel-plate Mode sets baking oven.Temperature is set as 40 DEG C, 50 DEG C, 60 DEG C, using the aftermentioned condition determination shown, entered with respective temperature Row tan δ measure.Determine after design temperature is reached, the value after reading 5 minutes is used as tan δ values.

In measure, will be above-mentioned above and below parallel-plate spacing be set to 0.5mm, deformation quantity be set to 10%, frequency for 50Hz come It is measured.In addition, the adjustment on determining temperature, the thermocouple set with the back side of the parallel-plate of in above-mentioned baking oven and downside Among, the thermocouple that the dorsal part of the parallel-plate of downside is set reaches the mode of specified temp to adjust oven temperature.

For the tan δ at the tan δ at the tan δ at 40 DEG C of gained, 50 DEG C, 60 DEG C, using temperature as transverse axis, with tan δ Painted as the longitudinal axis in the enterprising rower of icon, make chart.

52 mass % formalin 3500kg and 99 mass % phenol 2743kg are put into reactor, spiral shell is utilized The rotation revolving mixer of oar is stirred, and is adjusted the internal liquid temperature of reactor to 40 DEG C by tempering machine.Then, add Plus 50 mass % sodium hydrate aqueous solution untill the pH of reaction solution reaches 8.7.Reaction solution is warming up to by consuming for 1.5 hours Untill 85 DEG C, thereafter, 73 centistokes (=73 × 10 are reached in Ostwald's viscosity^-6m²/ s, the measured value at 25 DEG C) rank Section cooling reaction solution, addition urea 400kg.Thereafter, reaction solution is cooled to 30 DEG C, adds 50 matter of p-methyl benzenesulfonic acid monohydrate The % aqueous solution is measured untill pH reaches 6.4.Water by gained reaction solution with thin film evaporation machine concentration into phenolic resin Untill point rate reaches 7.4 mass %, as a result, the viscosity at 40 DEG C is 22000mPas.

The inventory of the formalin of 52 mass % shown in list of modification 1, the inventory of 99 mass % phenol, Ao Si Special Grindelwald viscosity, the addition of urea, using thin film evaporation machine to adjust the moisture rate in phenolic resin viscous at 40 DEG C to adjust Degree, it is in addition, same with phenol-formaldehyde A to operate, so as to obtain bakelite B~L.

[table 1]

(embodiment 1)

Relative to the mass parts of phenol-formaldehyde A 100, mixed using the ratio of 2.0 mass parts as surfactant with quality The block copolymer of epoxy ethane-epoxy propane of the ratiometer respectively containing 50 mass % and 50 mass % polyoxyethylene 12 The mixture of alkyl phenyl ether.Relative to the mass parts of phenolic resin 100 for being mixed with above-mentioned surfactant, addition table 2 is shown The mass parts of compound A 11, the mass % of xylene monosulfonic acid 80 as curing catalysts and the mass % of diethylene glycol 20 mixing The mass parts of thing 14, the mixing head using temperature adjustment to 25 DEG C is mixed, so as to obtain foaminess phenol resin composition.

Gained foaminess phenol resin composition is supplied to mobile facestock (lower facestock).On supplying to facestock Foaminess phenol resin composition, with contacting the surface of the surface of facestock for opposite side by other facestocks (upper facestock) covering, Clamped simultaneously with two facers, importing is heated in 85 DEG C of the first baking oven with strip type double type conveyer belt.Make After foaminess phenol resin composition was solidified with the holdup time of 15 minutes, it is made of 110 DEG C of curing oven 2 hours Phenol resin foam, so as to obtain being laminated with the phenol resin foam plywood of phenol resin foam in facestock.

It should illustrate, upper facestock and lower facestock have used glass fibre non-woven (trade name " Dura Glass Type (base weight is 70g/m to DH70²) ", Johns-Manville Corporation systems).

[table 2]

(embodiment 2)

Compound A is replaced using compound B, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound B 9, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 3)

Compound A is replaced using compound C, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound C 8.5, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 4)

Compound A is replaced using compound D, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound D 14, as upper facestock and lower facestock, use polyester non-woven fabrics (trade name " Spunbond E05030 Base weight is 30g/m²", Asahi Chemical Ind's system), in addition, operate similarly to Example 1, so as to obtain phenolic aldehyde tree Fat foaming body, phenol resin foam plywood.

(embodiment 5)

Compound A is replaced using compound E, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound E 6, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 6)

Compound A is replaced using compound F, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound F 8, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 7)

Compound A is replaced using compound G, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound G 11, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 8)

Bakelite B is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, the mass parts of addition compound A 11, as upper facestock and lower facestock, use polyester non-woven fabrics (trade name " Spunbond E05030 bases weight is 30g/m²", Asahi Chemical Ind's system), in addition, operate similarly to Example 1, so as to obtain Phenol resin foam, phenol resin foam plywood.

(embodiment 9)

Bakelite C is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, the mass parts of addition compound A 11, as upper facestock and lower facestock, use polyester non-woven fabrics (trade name " Spunbond E05030 bases weight is 30g/m²", Asahi Chemical Ind's system), in addition, operate similarly to Example 1, so as to obtain Phenol resin foam, phenol resin foam plywood.

(embodiment 10)

Phenolic resin D is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 12, operate, so as to obtain phenol resin foam, phenol similarly to Example 1 Urea formaldehyde foaming body plywood.

(embodiment 11)

Phenolic resin D is used as phenolic resin, compound A is replaced using compound F, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound F 6, in addition, are operated similarly to Example 1, so that Obtain phenol resin foam, phenol resin foam plywood.

(embodiment 12)

Phenolic resin E is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 12, operate, so as to obtain phenol resin foam, phenol similarly to Example 1 Urea formaldehyde foaming body plywood.

(embodiment 13)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound D, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound D 15, in addition, are operated similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 14)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound F, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound F 7, in addition, are operated similarly to Example 1, so that Obtain phenol resin foam, phenol resin foam plywood.

(embodiment 15)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound G, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound G 12, in addition, are operated similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 16)

Phenolic resin F is used as phenolic resin, compound A is replaced using compound B, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound B 9, as upper facestock and lower facestock, using polyester system without Spinning cloth, (" Spunbond E05030 bases weight is 30g/m to trade name²", Asahi Chemical Ind's system), in addition, with reality The equally operation of example 1 is applied, so as to obtain phenol resin foam, phenol resin foam plywood.

(embodiment 17)

Phenolic resin G is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 13, operate, so as to obtain phenol resin foam, phenol similarly to Example 1 Urea formaldehyde foaming body plywood.

(embodiment 18)

Compound A is replaced using compound H, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound H 7, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 19)

Compound A is replaced using compound I, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound I 11, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 20)

Compound A is replaced using compound J, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound J 11, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 21)

Compound A is replaced using compound K, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound K 11, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 22)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound L, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, add the mass parts of compound L 9, in addition, operate similarly to Example 1, so that Obtain phenol resin foam, phenol resin foam plywood.

(embodiment 23)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound M, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound M 9, in addition, are operated similarly to Example 1, so that Obtain phenol resin foam, phenol resin foam plywood.

(embodiment 24)

Compound A is replaced using compound N, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound N 10, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 25)

Phenolic resin E is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 10, operate, so as to obtain foaminess phenolic resin composition similarly to Example 1 Thing.By the foaminess phenol resin composition flow into the inside dimension that is covered by facestock of inner side be vertical 1000mm, horizontal 1000mm, Thick 1000mm aluminium-making mould inframe, and carry out closed.Will not expand around mould frame with upper and lower surface because of blow pressure The mode of exhibition is fixed with fixture.Importing is heated in 85 DEG C of baking oven, it is solidified 60 minutes.Thereafter, by phenolic aldehyde tree Fat foaming body takes out from mould frame, is heated 5 hours with 110 DEG C of baking ovens, so as to obtain the phenol resin foam of bulk.Made Facestock is same as Example 1.By the block phenol resin foam of gained from the central part of thickness direction with 50mm thickness Degree is cut into slices, so as to obtain the phenol resin foam of tabular.

(embodiment 26)

As upper facestock and lower facestock, having for a diameter of 0.5mm through hole is opened in use with the prior brill in 20mm interval Gas permeability and the aluminium flake strengthened with glass fibre, in addition, are operated similarly to Example 1, so as to obtain phenolic aldehyde tree Fat foaming body, phenol resin foam plywood.

(embodiment 27)

Relative to the mass parts of phenolic resin 100 for being mixed with surfactant, the silica of hexamethyl two of 2 mass parts is added Alkane, in addition, is operated similarly to Example 1, so as to obtain phenol resin foam, phenol resin foam plywood.

(embodiment 28)

Compound A is replaced using compound G, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus 2 mass parts HMDO, in addition, operate similarly to Example 1, thus obtain phenol resin foam, Phenol resin foam plywood.

(embodiment 29)

Compound A is replaced using compound I, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus 2 mass parts HMDO, in addition, operate similarly to Example 1, thus obtain phenol resin foam, Phenol resin foam plywood.

(embodiment 30)

Compound A is replaced using compound O, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound O 7, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, addition is used as plasticizer The mass parts of phthalic acid ester 1, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 31)

Compound A is replaced using compound P, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound P 7, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, addition is used as plasticizer The mass parts of phthalic acid ester 1, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 32)

Phenolic resin D is used as phenolic resin, compound A is replaced using compound O, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound O 7, relative to the phenolic aldehyde tree for being mixed with surfactant The mass parts of fat 100, add the mass parts of phthalic acid ester 1 as plasticizer, in addition, operate similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 33)

Compound A is replaced using compound Q, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound Q 7, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 34)

Phenolic resin E is used as phenolic resin, compound A is replaced using compound R, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, add the mass parts of compound R 9, relative to the phenolic aldehyde tree for being mixed with surfactant The mass parts of fat 100, add the mass parts of phthalic acid ester 1 as plasticizer, in addition, operate similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 35)

Phenolic resin F is used as phenolic resin, compound A is replaced using compound S, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound S 10, in addition, are operated similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 36)

Compound A is replaced using compound T, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound T 6, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, addition is used as plasticizer The mass parts of phthalic acid ester 1, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 37)

Compound A is replaced using compound U, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound U 7, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(embodiment 38)

Compound A is replaced using compound V, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound V 6, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, addition is used as plasticizer The mass parts of phthalic acid ester 1, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 39)

Bakelite B is used as phenolic resin, compound A is replaced using compound W, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound W 10, in addition, are operated similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 40)

Compound A is replaced using compound X, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound X 11, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, addition is used as plasticizer The mass parts of phthalic acid ester 1, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde tree Fat foaming body plywood.

(embodiment 41)

Phenolic resin F is used as phenolic resin, compound A is replaced using compound Y, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound Y 7, relative to the phenolic aldehyde tree for being mixed with surfactant The mass parts of fat 100, add the mass parts of phthalic acid ester 1 as plasticizer, in addition, operate similarly to Example 1, from And obtain phenol resin foam, phenol resin foam plywood.

(embodiment 42)

Compound A is replaced using compound Z, relative to the mass parts of phenolic resin 100 for being mixed with surfactant, is added Plus the mass parts of compound Z 10, in addition, operate similarly to Example 1, so as to obtain phenol resin foam, phenolic resin Foaming body plywood.

(comparative example 1)

Phenolic resin H is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, compound A11 mass parts are added, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde Foamed resin plywood.

(comparative example 2)

Phenolic resin I is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 11, operate, so as to obtain phenol resin foam, phenol similarly to Example 1 Urea formaldehyde foaming body plywood.

(comparative example 3)

Phenolic resin J is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, compound A11 mass parts are added, in addition, are operated similarly to Example 1, so as to obtain phenol resin foam, phenolic aldehyde Foamed resin plywood.

(comparative example 4)

Phenolic resin K is used as phenolic resin, relative to the mass of phenolic resin 100 for being mixed with surfactant Part, in addition the mass parts of addition compound A 10, operate, so as to obtain phenol resin foam, phenol similarly to Example 1 Urea formaldehyde foaming body plywood.

(comparative example 5)

Phenolic resin L is used as phenolic resin, compound A is replaced using compound B, relative to being mixed with surface The mass parts of phenolic resin 100 of activating agent, the mass parts of addition compound B 9, in addition, are operated similarly to Example 1, so that Obtain phenol resin foam, phenol resin foam plywood.

Resin and its characteristic, the chemical combination used in the phenol resin foam that will be obtained by above-described embodiment and comparative example The characteristic and evaluation result of thing and gained phenol resin foam are shown in table 3,4 and 5.

[table 3]

[table 4]

[table 5]

The phenol resin foam of embodiment 1~32 is relative to the excellent strength of compression, and the weight of heat-insulating material will not Become overweight, treatability is also excellent, construction when efficiency improve.In addition, used when phenol resin foam is fixed Part, framework are few, also excellent in terms of the cost in construction.

In addition, for ground, the construction of flat roof have the building of phenol resin foam, when in construction, maintenance When walking thereon, the problem of phenol resin foam of embodiment 1~32 will not also occur surface indentation or produce cracking.

On the other hand, the phenol resin foam of comparative example 1~5 is low relative to the compressive strength of density, relative to compression Intensity it is not enough.Especially, the separated foam rate of the phenol resin foam of comparative example 1,3~5 is low, thermal conductivity is also poor.

Industrial applicability

The load caused to environment of the phenol resin foam of present embodiment is small, compressive strength is high, and during construction Treatability and the cost expended when fixing are excellent, can be suitably employed in heat-insulating material of domestic use etc..

Claims

1. a kind of phenol resin foam, it is characterised in that containing selected from by chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogen It is at least one kind of in the group constituted for hydrocarbon,

Density is 20kg/m³Above and 100kg/m³Hereinafter,

Separated foam rate is more than 80% and less than 99%,

10% compressive strength meets the relation of following formula with the density,

C≥0.5X-7

In formula, C represents 10% compressive strength (N/cm²), X represents density (kg/m³)。

2. phenol resin foam according to claim 1, it contains the halogenated hydrocarbons and selected from by the chloro hydrogen It is at least one kind of in the group of fluoroolefins and the non-chloro HF hydrocarbon composition.

3. phenol resin foam according to claim 1 or 2, wherein, selected from by the chloro HF hydrocarbon and described It is at least one kind of for selected from by the chloro- 3,3,3- trifluoro propenes of 1-, the chloro- 3,3,3- trifluoros of 2- in the group of non-chloro HF hydrocarbon composition The group that propylene, 1,3,3,3- tetrafluoro-1-propenes, 2,3,3,3- tetrafluoro-1-propenes and 1,1,1,4,4,4- hexafluoro -2- butylene are constituted In it is at least one kind of.

4. according to phenol resin foam according to any one of claims 1 to 3, wherein, the halogenated hydrocarbons is isopropyl chloride.

5. according to phenol resin foam according to any one of claims 1 to 4, it is also comprising the hydrocarbon that carbon number is less than 6.

6. phenol resin foam according to claim 5, wherein, it is described to be selected from by chloro HF hydrocarbon, non-chloro hydrogen At least one kind of content in the group of fluoroolefins and halogenated hydrocarbons composition is relative to the chloro HF hydrocarbon, the non-chloro hydrogen fluorine The total amount for the hydrocarbon that alkene, the halogenated hydrocarbons and the carbon number are less than 6 is more than 30 mass %.

7. according to phenol resin foam according to any one of claims 1 to 6, it also includes nitrogen-containing compound.

8. phenol resin foam according to claim 7, wherein, the nitrogen-containing compound is selected from by urea, melamine Compound in the group that amine, quinuclidine, pyridine, hexa and their mixture are constituted.

9. according to phenol resin foam according to any one of claims 1 to 8, wherein, the chi after 3 drying and watering cycles repeatedly The absolute value of very little variable quantity is below 2.0mm.

10. according to phenol resin foam according to any one of claims 1 to 9, wherein, according to JIS A9511 (2003) 5.1.4 the fragility obtained is less than 50%.

11. a kind of phenol resin foam plywood, it is characterised in that in phenolic aldehyde according to any one of claims 1 to 10 There is facestock on 1st face of foamed resin and the 2nd face,

The facestock is respectively provided with gas permeability.

12. a kind of manufacture method of the phenol resin foam described in claim 1, it is characterised in that make in facestock containing Phenolic resin, surfactant, curing catalysts and selected from by chloro HF hydrocarbon, non-chloro HF hydrocarbon and halogenated hydrocarbons At least one kind of foaminess phenol resin composition in the group of composition is foamed and solidified,

The weight average molecular weight Mw for the phenolic resin obtained by gel permeation chromatography is more than 400 and less than 3000,

Viscosity at 40 DEG C of the phenolic resin is more than 1000mPas and below 100000mPas,

The viscosity rate of climb constant of the phenolic resin be 0.05 (1/ minute) more than and 0.5 (1/ minute) below.

13. the manufacture method of phenol resin foam according to claim 12, wherein, at 40 DEG C of the phenolic resin Losstangenttanδ be losstangenttanδ at more than 0.5 and less than 40.0, also, 60 DEG C be more than 2.0 and Less than 90.0.